Isomeric [RuCl2(dmso)2(indazole)2] complexes: ruthenium(II)-mediated coupling reaction of acetonitrile with 1H-indazole

Reaction of the antitumor complex trans-[Ru(III)Cl4(Hind)2]- (Hind = indazole) with an excess of dimethyl sulfoxide (dmso) in acetone afforded the complex trans,trans,trans-[Ru(II)Cl2(dmso)2(Hind)2] (1). Two other isomeric compounds trans,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (2) and cis,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (3) have been obtained on refluxing cis-[Ru(II)Cl(2)(dmso)(4)] with 2 equiv. of indazole in ethanol and methanol, respectively. Isomers 1 and 2 react with acetonitrile yielding the complexes trans-[Ru(II)Cl2(dmso)(Hind){HN=C(Me)ind}].CH3CN (4.CH3CN) and trans,cis-[Ru(II)Cl2(dmso)2{HN=C(Me)ind}].H2O (5.H2O), respectively, containing a cyclic amidine ligand resulting from insertion of the acetonitrile C triple bond N group in the N1-H bond of the N2-coordinated indazole ligand in the nomenclature used for 1H-indazole. These are the first examples of the metal-assisted iminoacylation of indazole. The products isolated have been characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, electrospray mass-spectrometry, thermogravimetry, differential scanning calorimetry, 1H NMR spectroscopy, and solid-state 13C CP MAS NMR spectroscopy. The isomeric structures of 1-3 and the presence of a chelating amidine ligand in 4 and 5 have been confirmed by X-ray crystallography. The electrochemical behavior of 1-5 and the formation of 5 have been studied by cyclic voltammetry.     

Tetrathiafulvalene‐Fused Porphyrins via Quinoxaline Linkers: Symmetric and Asymmetric Donor–Acceptor Systems

A tetrathiafulvalene (TTF) donor is annulated to porphyrins (P) via quinoxaline linkers to form novel symmetric P–TTF–P triads 1 a – c and asymmetric P–TTF dyads 2 a , b in good yields. These planar and extended π‐conjugated molecules absorb light over a wide region of the UV/Vis spectrum as a result of additional charge‐transfer excitations within the donor–acceptor assemblies. Quantum‐chemical calculations elucidate the nature of the electronically excited states. The compounds are electrochemically amphoteric and primarily exhibit low oxidation potentials. Cyclic voltammetric and spectroelectrochemical studies allow differentiation between the TTF and porphyrin sites with respect to the multiple redox processes occurring within these molecular assemblies. Transient absorption measurements give insight into the excited‐state events and deliver corresponding kinetic data. Femtosecond transient absorption spectra in benzonitrile may suggest the occurrence of fast charge separation from TTF to porphyrin in dyads 2 a , b but not in triads 1 a – c . Clear evidence for a photoinduced and relatively long lived charge‐separated state (385 ps lifetime) is obtained for a supramolecular coordination compound built from the ZnP–TTF dyad and a pyridine‐functionalized C₆₀ acceptor unit. This specific excited state results in a (ZnP–TTF)^?+ ??? (C₆₀py)^?? state. The binding constant of Zn^II ??? py is evaluated by constructing a Benesi–Hildebrand plot based on fluorescence data. This plot yields a binding constant K of 7.20×10⁴ M ^?1, which is remarkably high for bonding of pyridine to ZnP.     

Chiral separation of cathinone derivatives used as recreational drugs by cyclodextrin-modified capillary electrophoresis

In recent years, cathinone derivatives have entered the global drug market and caused serious social problems in many European countries. Modification of the basic structure of cathinone leads to a multitude of derivatives, including the most popular representative mephedrone. All those substances contain a stereogenic center and therefore two isoforms exist. As it is the case with many chiral active pharmaceutical ingredients, even the pharmacological effect of the enantiomers of those psychoactive compounds may differ. During this research, an easy-to-prepare chiral capillary zone electrophoresis method for the enantioseparation of a set of 19 cathinone derivatives was developed. Testing different types of cyclodextrin (CD), including native-β-CD, carboxymethyl-β-CD, 2-hydroxypropyl-β-CD, sulfated-β-CD, and native γ-CD, best results were obtained with the negatively charged sulfated-β-CD. The effect of the CD concentration, the temperature, and the addition of ACN to the BGE on the enantioseparation is shown by three model compounds. Under optimal conditions, using 20 mg/mL sulfated-β-CD in 50 mM ammonium acetate buffer pH?= 4.5 containing 10% v/v ACN at a cassette temperature of 40°C and with an applied voltage of 20 kV, all derivatives except methedrone were resolved in their enantiomers within 20 min.     

Metal Nanoparticles on Stainless Steel Surfaces as Novel Heterogeneous Catalysts

The goal of this work was the development of a novel type of heterogeneous catalyst, consisting of bare metal nanoparticles on stainless steel foils, which can be shaped to any kind of architecture and, if necessary, heated electrically. Solutions of pre-prepared, ligand protected and monodispersed gold, palladium, platinum and rhodium nanoparticles were sprayed onto stainless steel foils, followed by the careful removal of the ligand molecules by an oxygen plasma treatment. Due to this, bare particles become irreversibly fixed on the steel support. It could be shown that the original particle sizes do not change during the plasma treatment. Foils, densely coated with the nanoparticles, were used for gas phase catalyses in a self-made reactor at room temperature or at 60 °C. Hydrogenation of 1,3-butadiene at 15 nm Pd and 2 nm Pt, CO oxidation at 16 nm, 8 nm and 1.4 nm gold and NO reduction with NH₃ at 2 nm Rh particles were performed, indicating that the novel catalysts might in principle be applicable in technical processes if the experimental conditions like form and temperature would be optimized. Dedicated to Professor Dieter Fenske on the occassion of his 65th birthday.     

Physical and Chemical Consequences of Size-Reduction of Gold: Bioresponse and Biodistribution

The article is dealing with the dependency of physical and chemical properties on size and coating of gold nanoparticles (Au NPs) and their potential in medicine. Full-shell clusters of the type Au₅₅(PR₃)₁₂Cl₆ are in the focal point due to their special properties. They act as quantum dots at room temperature and their stability is based on the perfect cuboctahedral structure. The bioresponse of the 1.4 nm Au₅₅ clusters is, compared with smaller and larger Au NPs, very special, indicated by high cytotoxicity. It is caused by oxidative stress in cells accompanied by direct interactions with DNA. Biodistribution in Wistar–Kyoto rats differs also characteristically from larger Au NPs. Larger Au NPs, intravenously injected, assemble almost quantitatively in the liver, whereas Au₅₅ clusters distribute over numerous other organs. All comparisons have been carried out by Au species with identical ligand molecules in order to have the same conditions concerning surface behaviour.     

A general and efficient pseudopotential Fourier filtering scheme for real space methods using mask functions

A scheme for the Fourier filtering of pseudopotentials in real space calculations is proposed, in order to reduce the artifact of positional energy dependence ("egg box" effect). It is based on an improved version of the mask function method poposed by Wang [Phys. Rev. B 64, 201107/1 (2001)]. It is easy to implement, efficient, and accurate. By using atom-centered compensation charges, the local part of the pseudopotential becomes short ranged and can be filtered on the same footing as the nonlocal parts. A major advantage of the approach is that a generic set of parameters can be used for different pseudopotentials. A balanced parameter set is derived and validated. In this context a strategy to monitor the extent of grid dependence is introduced. It is found that, given a sufficiently fine grid spacing is used to represent the atomic valence density, the positional energy dependence can be reduced below 0.1 mhartree for all investigated atoms. On the example of a D(3h) symmetric Si(5) cluster and the C(60) molecule it is demonstrated that the artificial symmetry breaking of both bond lengths and orbital energies can substantially be reduced by the filtering scheme.     

Angular Benzoperylenetetracarboxylic Bisimides

Benzoperylene derivatives with two angularly attached dicarboxylic imide rings, which were prepared by the Diels–Alder‐Reaction, exhibit strong fluorescence and their free peri positions allow either control of the UV/Vis spectra through their substituents or form anchor positions for the attachment of functional units. The angular chromophore 3 may be used both for fluorescent labeling such as for primary amines or enzymes or as building blocks for more complex assemblies where they may act as energy donors for FRET or electron acceptors in PET such as for photovoltaic solar cells.     

Convergent beam electron diffraction study of Pb2CoWO6 at 100 K

A study by convergent beam electron diffraction has been performed in order to clarify the symmetry of the phase III of Pb₂CoWO₆. Microdiffractions with higher-order Laue zone on monodomain areas have confirmed the cell proposed in our preceding study. In addition, an ‘axial’ glide plane (c) has been found normal to the b axis. In the conditions of observation, the convergent beam electron diffraction patterns lead to an apparent point group mmm. No breakdown of a mirror symmetry could be found. The discrepancy between this result and the existence of a spontaneous polarisation is discussed.     

Polarized light microscopy of the ferroelastic domains of YBa2Cu3O7−x

A short overview is given on recent polarized light microscopy studies of the orthorhombic ferroelastic domains and domain structures of YBa₂Cu₃O_7-x . The optical characteristics of large domains and lamellar domains with a high density of twin walls are pointed out, both for reflected and transmitted light. The polarizing microscope has allowed to observe the ferroelastic detwinning in situ and to determine the activation energy of the ferroelastic wall movements. The question of a potential ferroelectric phase transition is also discussed.